JPH0748459A - Ionic conductive thin film and production thereof - Google Patents

Abstract

PURPOSE:To obtain the pinhole-free thin film, capable of forming a film having a thickness in the order of Angstrom and controlling the film thickness and high in transparency by bringing a substrate surface into contact with a specific chemical adsorbent molecule, carrying out the condensing reaction and introducing the specified molecule and ions thereinto. CONSTITUTION:This conductive thin film is obtained by bringing a substrate surface having active H or an alkali metal on the surface or applying the active H or alkali metal to the surface thereof into contact with a chemical adsorbent molecule containing any one of functional groups expressed by the formula AX (A is Si, Ge, etc.; X is a halogen, cyano, etc.), etc., formula I (A' is N or O), formula II or III, carrying out the condensing reaction, covalently bonding the adsorbent molecule onto the substrate, forming a chemical adsorbent film, then introducing a molecule containing ether bond, sulfide bond, etc., into the resultant adsorbent film, fixing the molecule thereto and subsequently introducing at least one ion expressed by the formula M<n+> [M is an alkaline (earth) metal, Cu, etc.; (n) is 1 or 2] and X<-> (X is a halogen, CF3SO3, ClO4, etc.) into the adsorbent film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductive thin film and a method for manufacturing the same. More specifically, the present invention relates to an ion conductive thin film in which a chemical adsorption film provided on a substrate contains a specific bond or a functional group and ions and has ion conductivity, and a method for producing the same.

[0002]

2. Description of the Related Art Ionic conductivity means that ions serve as charge carriers and have high electrical conductivity. Particularly generally, it refers to a case where the conductivity is equal to or higher than that of saline or dilute sulfuric acid.

A typical substance having ionic conductivity is a solution in which an electrolyte is dissolved in a liquid, and is widely used in devices utilizing an electrochemical reaction, such as batteries and electrolytic capacitors. Depending on the type of charge carrier, it is divided into cation conductors and anion conductors. The former is mainly alkali, silver, and copper ions and proton conductors, and the latter is mainly fluoride and oxide ion conductors. Is.

On the other hand, solid substances having high ionic conductivity can be roughly classified into two types. One is a group called an inorganic solid electrolyte, for example, Na-β-Al ₂
O ₃ and Na _{1 + n} Zr ₂ P _3-n SinO ₁₂ (0 ≦ n ≦ 3)
Have good ionic conductivity. Journal of Chemical Physics Vol. 54, p. 414 (M.
S. Whttingham et. Al., J. Chem. Phys., 54, 414 (1
971)). The above conductor has already been applied to the all-solid-state secondary battery disclosed in JP-A-3-297068 and the combustion display device disclosed in JP-A-55-123920.

The other is a dispersion of an ionic additive in an organic polymer, such as polyethylene oxide (hereinafter abbreviated as PEO) or polypropylene oxide (hereinafter P.
A complex of a polyether such as PO (abbreviated as PO) and various kinds of alkali metal salts is described in Fast Ion Transport in Solid, page 131 (P. Vashista eta).
l., Fast Ion Transport in Solids, 131, North-Holla
nd, New York (1979)), and a composite membrane of polyacrylonitrile with LiClO ₄ and ethylene carbonate was reported by Journal of Polymer Science (J. Poly).
m. Sci., A2, 21, 939 (1983)).
It has been confirmed that these systems have viscoelasticity and flexibility peculiar to organic polymers, and therefore can adapt to the volume change that occurs during the ion-electron exchange process with the electrode. Also,
Since it has good processability and storage stability, it has already been used in various applications. However, for example, although it is applied to an electrochemical color-developing element or the like disclosed in JP-A-3-231229, it has low ionic conductivity to reach a practical element, and thus, like the solid electrolyte disclosed in JP-A-3-129603. In order to improve the ionic conductivity, it is combined with an inorganic solid electrolyte or a crosslinked polymer film is impregnated with an electrolyte solution as in the organic secondary battery disclosed in JP-A-63-164176.

It is easy to determine that the resistance value of a substance having a small ionic conductivity as described above can be lowered if it can be made into a thin film. In the past, it was general that the film was thinned by the casting method, but recently, JP-A-2-26226.
A method for forming a thin film by an RF sputtering method such as the thin film ion-conductive coating described in Japanese Patent No. 7 or a method for forming a thin film by plasma polymerization (Z. Ogumi et al., Che.
m. Lett., 1988, 1811 (1988)) has been tried. However, the thickness of the thin film formed by these methods is μ
The limit is the m-order, and if it is thinner than that, pinholes will occur. This point was also difficult to form into a thin film because the synthesis temperature of the inorganic solid electrolyte was high and the alkali metal oxide was evaporated during the formation of the thin film to make it difficult to control the composition.

As described above, at present, there is no report of a thin film having an ionic conductivity and having an angstrom order thickness.

[0008]

The conventional electrolyte solution is
A solution in which an electrolyte is dissolved in water or an organic solvent,
Therefore, there were many problems due to the liquid state.

For example, it is difficult to reduce the size and simplification because a container to be stored is indispensable. Moreover, even if it was stored in the container, it was necessary to take measures to prevent liquid leakage. Further, it is highly corrosive and has a problem in durability.

Further, in the conventional solid electrolyte in which the above-mentioned drawbacks have been improved to some extent, it is fatal that a special crystal structure is required, processing is difficult, and mechanical strength is extremely weak. It was a physical problem.

In the case where the ionic additive is dispersed in the organic polymer, all of the above-mentioned drawbacks have been eliminated, but the greatest drawback is that the ionic conductivity is small at the present level. . In particular, the ionic conductivity of this system is highly temperature-dependent. For example, in a system in which metal ions are dispersed in PEO, good ionic conductivity of about 10 ^-3 S / m at 80 ° C is shown, but near room temperature. It was markedly low. Therefore, it was difficult to incorporate it into a versatile device that can be used in a wide temperature range.

However, as described above, even if a substance having a small ionic conductivity can be made thin, the resistance value can be lowered, and therefore thinning is being actively studied. According to the current method, the limit is on the order of μm, and if it is made thinner than that, pinholes are generated and ionic conduction cannot be obtained.

In order to solve the above-mentioned conventional problems, the present invention is capable of forming a film having a thickness on the order of angstroms and controlling the film thickness. Therefore, it has good transparency, is pinhole-free, and is firmly bonded to a substrate. It is an object of the present invention to provide an ion conductive thin film and a manufacturing method thereof.

[0014]

To achieve the above object, the ion conductive thin film of the present invention is a chemisorption film formed by covalent bonds with the surface of a substrate, which is an ether bond, a sulfide bond or an ester bond. , Amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group, phosphonyl group (-P
O ₂ −), a phosphinyl group (—PO—), a sulfonyl group (—SO ₂ —), and a sulfinyl group (—SO—), and at least one bond or a functional group, and the above formula (Formula 1) And at least one ion selected from the above formula (Formula 2) and having ion conductivity. In the above structure, the chemisorption film is preferably a monomolecular film. Further, in the above structure, the chemisorption film is preferably a monomolecular cumulative film.

Next, the first method for producing the ion-conductive thin film of the present invention comprises the step of adding the above formula (Chemical Formula 3) to the surface of a substrate having or imparting active hydrogen or alkali metal to the surface.
And a functional group represented by the formula (Formula 4),
A halogenated sulfonyl group represented by the above formula (Formula 5),
And a chemisorptive molecule containing at least one functional group selected from the halogenated sulfinyl groups represented by the formula (Formula 6) is brought into contact with each other to cause a condensation reaction to covalently bond the chemisorptive molecule onto the substrate. After forming a chemisorption film, then ether bond, sulfide bond, ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group,
Phosphonyl group (-PO ₂ -), a phosphinyl group (-P
O-), sulfonyl groups (-SO ₂ -), and a molecule containing at least one bond or functional group selected from sulfinyl group (-SO-) is introduced and fixed in the chemically adsorbed film, then the formula (Formula 7) and at least one ion selected from the formula (Formula 8) is introduced into the chemisorption film.

Next, the second method for producing the ion conductive thin film of the present invention is the same as the above formula (Formula 9) on the surface of a substrate having or imparting active hydrogen or alkali metal to the surface.
Selected from a functional group represented by the formula, a functional group represented by the formula (Formula 10), a halogenated sulfonyl group represented by the formula (Formula 11), a halogenated sulfinyl group represented by the formula (Formula 12), and a hydroxyl group. At least one functional group,
And ether bond, sulfide bond, ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group, phosphonyl group (—PO ₂ —), phosphinyl group (—PO— ),
Sulfonyl group (-SO ₂ -), a sulfinyl group (-S
A chemisorption molecule containing at least one bond or a functional group selected from O-) is brought into contact with the substrate to cause a condensation reaction to covalently bond and immobilize the chemisorption molecule on the substrate, and then the above formula It is characterized in that the ions represented by the chemical formula 13 or the chemical formula 14 are introduced into the chemical adsorption film.

Next, the third method for producing the ion conductive thin film of the present invention is the same as the above formula (Chemical Formula 1) on the surface of a substrate having or imparting active hydrogen or alkali metal on the surface.
5), a functional group represented by the formula (Formula 16), a halogenated sulfonyl group represented by the formula (Formula 17), a halogenated sulfinyl group represented by the formula (Formula 18) and a hydroxyl group. A chemisorption molecule containing at least one selected functional group is brought into contact with each other to cause a condensation reaction to immobilize the molecule on the substrate to form a chemisorption film, and then to the chemisorption film with an ether bond or a sulfide bond. , Ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group, phosphonyl group (-PO _2- ),
Phosphinyl group (-PO-), sulfonyl group (-SO
_2- ) and at least one bond or functional group selected from a sulfinyl group (-SO-) is introduced or generated, and then an ion selected from the above formula (Formula 19) and the above formula (Formula 20) is added to the above chemical formula. It is characterized in that it is introduced into the adsorption film.

According to the structure of the first to third manufacturing methods of the present invention, the method of introducing ions into the chemisorption film is as follows:
It is preferably carried out by immersing in a solution containing the ions represented by the formula (Formula 21) or the formula (Formula 22).

[0019]

According to the above-described structure of the present invention, it is possible to form a film having a thickness on the order of angstroms and to control the film thickness. Therefore, the transparency is good, the pinhole is free, and the ions are firmly bonded to the substrate. It can be a conductive thin film. That is, according to the present invention, an ionic conductive ether bond, sulfide bond, ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group, phosphonyl group ( -PO ₂ -), a phosphinyl group (-PO-),
Sulfonyl group (-SO ₂ -), a sulfinyl group (-S
The molecule having at least one bond or functional group selected from O-) is at least one selected from Si, Ge, Sn, Ti, Zr, S and C directly with the substrate or indirectly through the inner layer film. Since it is covalently bonded via an atom, it is extremely thin and has excellent ionic conductivity. Furthermore, not only the transparency and durability are maintained, but also excellent ionic conductivity can be imparted without damaging the substrate.

When the ion conductive thin film is a monomolecular film or a monomolecular cumulative film, the film thickness can be uniform. Next, according to the inventions of the first to third production methods of the present invention, it becomes possible to efficiently and rationally produce a thin film having ion conductivity.

[0021]

EXAMPLES The present invention will be described in more detail below with reference to examples. The ion conductive thin film of the present invention is firmly fixed to a substrate directly or indirectly through an inner layer by a covalent bond, and in principle, film formation and film thickness control in the angstrom order are possible, and therefore it is transparent. An ion conductive thin film having good properties and free of pinholes.

By the way, as a thin film capable of forming a film on the order of angstrom and controlling the film thickness, a film formed by the Langmuir-Blodgett (LB) method and the chemical adsorption method is currently effective. However, the basic idea of the present invention relating to ionic conduction is that the ions move due to the segmental motion of the membrane constituent molecules and the electric charge is carried without the membrane constituent molecules themselves moving, so that the membrane is firmly fixed to the substrate. Need to be. For that purpose, it can be said that the film formed by the chemical adsorption method in which it is fixed to the substrate by covalent bond is more suitable.

The basic technique of the chemisorption method is described in Journal of American Chemical Society No. 1
Volume 02, page 92 (J. Sagiv, J. Am. Chm. Soc., 102,
92 (1980)) and Langmuir Vol. 6, page 851 (K. Ogawa et al., Langmuir, 6, 851 (1990)). This chemical adsorption method is a method of immobilizing a molecule called a chemical adsorbent having a chlorosilyl group on a substrate having a hydroxyl group on its surface through a dehydrochlorination reaction.

As the chemical adsorbent, the functional group represented by the formula (Formula 3), the functional group represented by the formula (Formula 4), the halogenated sulfonyl group represented by the formula (Formula 5), the formula (Formula 5) A molecule having at least one functional group selected from the halogenated sulfinyl group and the cyano group (—CN) represented by Chemical formula 6) can be formed, but is not limited thereto. However, the halogen referred to here includes Cl, Br or I, but Cl is preferable from the viewpoint of reactivity, but the same chemisorption film can be obtained even with Br or I.

As the substrate on which the chemisorption film is fixed, a hydroxyl group, a carboxyl group, a sulfinic acid group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, a quaternary ammonium group, a quaternary ammonium group, a At least one functional group and / or hydroxyl group selected from quaternary phosphonium group, thiol group and amino group, carboxyl group, sulfinic acid group, sulfonic acid group, phosphoric acid group, phosphorous acid group, quaternary ammonium group, Quaternary phosphonium group, thiol group,
H having at least one functional group selected from the functional groups in which H of at least one functional group selected from an amino group is substituted with an alkali metal or an alkaline earth metal,
And already immobilized on a substrate having the functional groups described above,
In addition, examples thereof include a chemisorption film having the above-mentioned functional group on the film, but it is not limited to these.

When the surface of the substrate has no or a small amount of the above-mentioned functional groups, UV / ozone treatment, oxygen plasma treatment, treatment with a compound oxidant such as potassium permanganate solution is carried out to modify the surface, It is effective to create or increase functional groups. As a method for fixing the chemical adsorption film to the substrate, there is a method of bringing the substrate into contact with the liquid and / or gaseous chemical adsorbent or a solution in which the chemical adsorbent is dissolved. Of course, it is not limited.

When provided as a solution, the solvent used is preferably composed of molecules containing no active hydrogen. For example, when the chemical adsorbent has a long-chain alkyl group, a mixed solvent of hydrocarbons and halogenated carbons is used. When the chemical adsorbent has a carbonyl group, halogenated hydrocarbons and aromatics are used. It is suitable to use,
Of course, it is not limited to these.

After fixing the chemisorption film on the substrate,
It is preferable to add a step of removing unreacted molecules because it is easy to form a monomolecular film and a monomolecular cumulative film. An aprotic solvent is preferable as the solvent used for the washing and removal. For example, halogenated carbons, ethers, lactones, esters, nitriles, amides and the like can be mentioned, but it goes without saying that they are not limited to these.

There are basically three methods as the types of manufacturing steps before the introduction of ions in the ion conductive chemisorption film. One of them is a bond or a functional group having ion conductivity, that is, an ether bond, a sulfide bond, an ester bond, an amino group, a phosphoric acid group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfonic acid group, a quaternary ammonium group, phosphonyl group (-PO ₂ -), a phosphinyl group (-PO-), a sulfonyl group (-SO ₂ -), including chemical adsorbent having at least one bond or functional group selected from the sulfinyl group (-SO-) A method of forming a chemisorption film by using the following method is as follows. First, a chemisorption film is formed, and a molecule having a bond or a functional group having ion conductivity by a chemical reaction is formed on the surface of the chemisorption film. Another way is to fix it
First, a chemical adsorption film is formed, and a chemical reaction is caused on the chemical adsorption film to create a bond or a functional group having ion conductivity.

Examples of the ions introduced into the chemisorption film formed by the above method include the ions represented by the above formula (Formula 1) or the above formula (Formula 2), but not limited to these. Of course.

Regarding the method of introducing the ions,
The method of immersing the substrate having the chemisorption film in the solution containing the ions or the ion implantation method is suitable, but the method is not limited to these.

When a method of immersing a substrate having a chemisorption film in a solution containing the ions is used as the method of introducing the ions, the ions are LiI and CF ₃ SO 4.
₃ Li, LiClO ₄ , LiBF ₄ , LiPF ₆ , Li
SCN, LiAsF ₆ , AgI, CF ₃ SO ₃ Ag, A
_{gClO 4, AgBF 4, AgPF 6} , AgSCN, A
It is suitable to introduce by dissolving a salt such as gAsF ₆ in water or the like, but it goes without saying that usable salts are not limited to these.

Further, the conductivity can be improved by incorporating a polar solvent such as water into the ion conductive thin film of the present invention. Hereinafter, the ion conductive thin film of the present invention and the method for producing the same will be described in more detail. However, the present invention is not limited to the following specific examples.

Example 1 First, an adsorption solution A was prepared. Repeated distillation several times in the presence of metallic sodium,
About 1 vol. Of carbomethoxyethyltrichlorosilane, which is a chemical adsorbent, was added to toluene with water removed as much as possible. It was dissolved at a concentration of%, and this was designated as adsorption solution A.

A substrate having aluminum vapor-deposited on glass was washed with an organic solvent and then subjected to UV / ozone treatment for 10 minutes to form a substrate on which a very thin oxide layer was formed. The substrate was immersed in the adsorption solution A for 1 hour. By this treatment, the -OH group of the oxide layer on the aluminum surface and the silyl group of carbomethoxyethyltrichlorosilane undergo a dehydrochlorination reaction to form a covalent bond. Subsequently, the unreacted chemical adsorbent was removed by washing with toluene for 10 minutes. It was then reacted with water. By this treatment, the chemisorption monomolecular film 1 as shown in FIG. 1 could be formed.

The formation of the chemisorption monolayer 1 is as follows.
By the Fourier transform infrared absorption (FTIR) spectroscopy, 2920,2860 (attributable: -CH ₂ -), 174
0 (attribute: C = O), 1080 (attribute: Si-O) cm
This was confirmed by the fact that a signal characteristic of this structure was obtained at ^-1 .

Next, the substrate having the chemisorption monomolecular film 1 was immersed in 100 ° C. for 5 hours in polyethylene glycol monomethyl ether having an average molecular weight of 350 (abbreviation: PEO350) to which a very small amount of sulfuric acid was added. Then 1
Unreacted PEO350 was removed by washing with water for 0 minutes. By this treatment, a chemisorption monomolecular cumulative film 2 having a poly (alkylene ether) group as shown in FIG. 2 was formed. In FIG. 2, n indicates the degree of polymerization.

The formation of the chemisorption monomolecular cumulative film 2 was 2920, 286 by FTIR spectrum measurement.
It was confirmed that the signal at 0 (attribution: —CH ₂ —) cm ⁻¹ increased, and a signal characteristic of this structure was newly obtained at 1140 (attribute: C—O—C) cm ⁻¹ . .

[0039] 1wt of LiClO ₄ the substrate having the chemisorption monomolecular film 2. % Acetone solution for several minutes, then pulled out of the solution and dried. By this treatment, LiClO ₄ was added to the chemisorption monomolecular cumulative film 2 to form Li
/ Ethylene oxide repeating unit = 0.1 was introduced.

The introduction of LiClO ₄ was carried out by FTI.
1150 (attribution: Cl
It was confirmed that a signal characteristic of this structure was obtained at -O) cm ^-1 .

On the substrate having the chemically adsorbed monomolecular cumulative film 2 into which LiClO ₄ was introduced, 1 mm was obtained under a vacuum of 10 ⁻⁵ Torr.
A x 1 mm aluminum top electrode was deposited. Attach a lead wire to this upper electrode and aluminum of the substrate, and
Equivalent parallel capacitance and equivalent parallel resistance were measured with an R meter.
As a result, the capacity at 1 MHz is 1.8 × 10 ⁻⁸ F,
The resistance value was 20Ω. Since the film thickness of the chemisorption monomolecular cumulative film 2 obtained by ellipsometry is 2 × 10 ⁻⁹ m, the resistance value of 20Ω corresponds to 1 × 10 ⁻⁶ Scm ⁻¹ .

Example 2 In the same manner as in Example 1, the adsorption solution A and the substrate were prepared, and then the chemisorption monomolecular film 1 was prepared.
Was formed.

The formation of the chemisorption monolayer 1 is as follows.
It was also confirmed that the signal characteristic of this structure was obtained by FTIR spectrum measurement. Next, the substrate having the chemisorption monolayer 1 was treated with polyethylene glycol monomethyl ether (abbreviation: PEO75) having an average molecular weight of 750.
It was immersed for 5 hours at 100 ° C. in 0) to which a very small amount of sulfuric acid was added. Subsequently, washing with water was performed for 10 minutes to remove unreacted PEO750. By this treatment, a chemisorption monomolecular cumulative film 3 having a poly (alkylene ether) group as shown in FIG. 3 was formed. In FIG. 3, m indicates the degree of polymerization.

The formation of this chemisorption monomolecular cumulative film 3 was 2920, 286 by FTIR spectrum measurement.
It was confirmed that the signal at 0 (attribution: —CH ₂ —) cm ⁻¹ increased, and a signal characteristic of this structure was newly obtained at 1140 (attribute: C—O—C) cm ⁻¹ . .

[0045] 1wt of LiClO ₄ the substrate having the chemisorption monomolecular film 3. % Acetone solution for several minutes, then pulled out of the solution and dried. By this treatment, LiClO ₄ was added to the chemisorption monomolecular cumulative film 3 to form Li
/ Ethylene oxide repeating unit = 0.1 was introduced.

The introduction of LiClO ₄ was carried out by FTI.
1150 (attribution: Cl
It was confirmed that a signal characteristic of this structure was obtained at -O) cm ^-1 .

This LiClO_FourAdsorbed chemisorption
10 on the substrate having the child accumulation film 3^-Five1 under vacuum at Torr
A mm x 1 mm aluminum top electrode was deposited. this
Attach the lead wire to the upper electrode and aluminum of the substrate,
Measure the equivalent parallel capacitance and equivalent parallel resistance with the LCR meter.
It was As a result, the capacity at 1 MHz is 2.2 x 10 ^-8
F, the resistance value was 24Ω. Requested by ellipsometry
The total thickness of the chemisorption monomolecular cumulative film 3 is 3.2 × 10.^-9m
Therefore, the resistance value of 24Ω is 7.5 × 10.^-7Scm^-1To
Equivalent to.

(Embodiment 3) First, in the same manner as in Embodiment 2,
A chemisorption monomolecular cumulative film 3 was formed. The formation of the chemisorption monomolecular cumulative film 3 could be confirmed by obtaining a signal characteristic of this structure by FTIR spectrum measurement.

The substrate having the chemisorption monomolecular cumulative film 3 was made of CF ₃ SO ₃ Li of 1 wt. % Acetone solution for several minutes, then pulled out of the solution and dried. By this treatment, CF ₃ SO ₃ Li was introduced into the chemisorption monomolecular cumulative film 3 at a ratio of Li / ethylene oxide repeating unit = 0.2.

The introduction of CF ₃ SO ₃ Li is F
A new 1350 (attribution:
It was confirmed that a signal characteristic of this structure was obtained at O = S = O) and 1320 (attribution: CF ₃ ) cm ⁻¹ .

This CF₃SO₃Chemisorption with introduction of Li
10 on the substrate having the monomolecular cumulative film 3 ^-FiveUnder vacuum of Torr
Then, a 1 mm × 1 mm aluminum upper electrode was vapor-deposited.
Attach the lead wire to this upper electrode and aluminum of the substrate
Measure the equivalent parallel capacitance and equivalent parallel resistance with the LCR meter.
Decided As a result, the capacity at 1 MHz is 2.6 x 1
0^-8F, the resistance value was 29Ω. Ellipsometry
The film thickness of the chemisorption monomolecular cumulative film 3 obtained was 3.2 × 10
^-9Therefore, the resistance value of 29Ω is 9.1 × 10. ^-7Scm
^-1Equivalent to.

Under the same conditions as in Examples 1 to 3 described above, a similar ion conductive thin film was formed by using the ions, the functional groups and the bonds listed in claim 1 and the functional groups listed in claim 2. I was able to manufacture.

As explained above, the ion conductive membrane of the present invention has sufficient ion conductivity for practical use,
Therefore, the practicability of the ion conductive thin film of the present invention is extremely high. For example, it can be used for ultra-compact and lightweight primary batteries, secondary batteries, electrolytic capacitors, sensors, electrochromic display elements and the like.

On the other hand, the thin film of the present invention can be formed as long as hydrogen, an alkali metal and / or an alkaline earth metal which are active in principle are present on the surface of the substrate. Nevertheless, the ion-conducting thin film of the present invention can be used in applications where it is difficult to do so chemically or under various circumstances. In particular, it can be sufficiently used for applications aiming at downsizing and weight reduction, for example.

[0055]

As described above, according to the present invention, an ether bond, a sulfide bond, an ester bond, an amino group, a phosphoric acid group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfonic acid group, a quaternary ammonium group, phosphonyl group (-PO ₂ -), a phosphinyl group (-PO-), a sulfonyl group (-SO ₂ -), and a sulfinyl group (-
A chemical adsorption film containing at least one bond or functional group selected from SO-), containing at least one ion selected from the general formula (Formula 1) and the general formula (Formula 2), and having ion conductivity. By doing so, it is possible to form a film having a thickness on the order of angstroms and control the film thickness, and therefore, it is possible to obtain an ion conductive thin film that has good transparency, is pinhole-free, and is firmly bonded to the substrate.

Further, according to the first to third production methods of the present invention, it is possible to form an angstrom-order film and control the film thickness, and to obtain a pinhole-free and ion-conductive thin film that is firmly bonded to the substrate. It becomes possible to manufacture efficiently and rationally.

[Brief description of drawings]

FIG. 1 is an enlarged view of a main part of a chemisorption monolayer according to a first embodiment of the present invention.

FIG. 2 is an enlarged view of a main part of the chemisorption monomolecular cumulative film of Example 1 of the present invention.

FIG. 3 is an enlarged view of a main part of a chemisorption monomolecular cumulative film of Examples 2 to 3 of the present invention.

[Explanation of symbols]

1 Chemisorption monomolecular film 2 Chemisorption monomolecular cumulative film having poly (alkylene ether) group 3 Chemisorption monomolecular cumulative film having poly (alkylene ether) group

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazufumi Ogawa 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (10)

[Claims] 1. A chemisorption film formed by a covalent bond with a substrate surface, which comprises an ether bond, a sulfide bond, an ester bond, an amino group, a phosphoric acid group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfonic acid group, quaternary ammonium group, phosphonyl group (-PO ₂ -), a phosphinyl group (-PO-), a sulfonyl group (-SO ₂ -),
And at least one bond or functional group selected from a sulfinyl group (-SO-), and at least one ion selected from the general formula (Formula 1) and the general formula (Formula 2), and having ion conductivity. An ion-conducting thin film having. [Chemical 1] [Chemical 2] 2. The chemisorption film is a monomolecular film.
The ion-conducting thin film according to 1. 3. The ion conductive thin film according to claim 1, wherein the chemisorption film is a monomolecular cumulative film. 4. The surface of a substrate having or imparting active hydrogen or an alkali metal to the surface thereof has the general formula (Chemical Formula 3)
And a functional group represented by the general formula (Formula 4),
A halogenated sulfonyl group represented by the general formula (Formula 5),
And a chemisorption molecule containing at least one functional group selected from the halogenated sulfinyl groups represented by the general formula (Chemical Formula 6) is brought into contact to cause a condensation reaction to covalently bond the chemisorption molecule onto the substrate. After forming a chemisorption film, then ether bond, sulfide bond, ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group,
Phosphonyl group (-PO ₂ -), a phosphinyl group (-P
O-), sulfonyl groups (-SO ₂ -), and a molecule containing at least one bond or functional group selected from sulfinyl group (-SO-) is introduced and fixed in the chemically adsorbed film, then the general formula (Formula 7) and at least one ion selected from the general formula (Formula 8) is introduced into the chemisorption film. [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] 5. The surface of a substrate having or imparting active hydrogen or an alkali metal to the surface has the general formula:
Selected from a functional group represented by the formula, a functional group represented by the general formula (Formula 10), a halogenated sulfonyl group represented by the general formula (Formula 11), a halogenated sulfinyl group represented by the general formula (Formula 12), and a hydroxyl group. At least one functional group,
And ether bond, sulfide bond, ester bond, amino group, phosphoric acid group, hydroxyl group, mercapto group, carboxyl group, sulfonic acid group, quaternary ammonium group, phosphonyl group (—PO ₂ —), phosphinyl group (—PO— ),
Sulfonyl group (-SO ₂ -), a sulfinyl group (-S
A chemisorption molecule having at least one bond or a functional group selected from O-) is brought into contact with the substrate to cause a condensation reaction to covalently bond and immobilize the chemisorption molecule on the substrate, and then the general formula A method for producing an ion conductive thin film, which comprises introducing the ions represented by (Chemical Formula 13) or the general formula (Chemical Formula 14) into the chemical adsorption film. [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12] [Chemical 13] [Chemical 14] 6. Surface-active hydrogen or alkali metal
On the surface of the substrate having or imparting
5) Functional group represented by the general formula (Chemical Formula 16)
Noh group, halogenated sulfo represented by the general formula (Chem. 17)
Nyl group, halogenated sulfol represented by the general formula (Formula 18)
At least one functional group selected from an inynyl group and a hydroxyl group
Contacting a chemisorption molecule containing a group to cause a condensation reaction
To fix the molecule on the substrate to form a chemisorption film.
Formed on the chemisorptive film, and then the ether bond
Bond, ester bond, amino group, phosphate group, hydroxyl group
Group, mercapto group, carboxyl group, sulfonic acid group,
Quaternary ammonium group, phosphonyl group (-PO₂-),
Phosphinyl group (-PO-), sulfonyl group (-SO
₂-), And a sulfinyl group (-SO-)
Introducing at least one bond or functional group, or
Is generated, and then the general formula (formula 19) and the general formula (formula 2)
Ions selected from 0) are introduced into the chemisorption film.
A method for producing an ion conductive thin film, comprising: [Chemical 15][Chemical 16][Chemical 17][Chemical 18][Chemical 19][Chemical 20] 7. The method for introducing ions into the chemisorption film is carried out by immersing in a solution containing the ions represented by the general formula (Formula 21) or (Formula 22). The method for producing the ion-conductive thin film according to 1. [Chemical 21] [Chemical formula 22] 8. The method for introducing ions into the chemisorption film according to claim 4, 5 or 6, wherein the ions represented by the general formula (Chemical formula 23) or the general formula (Chemical formula 24) are ion-implanted. Method for producing ion conductive thin film. [Chemical formula 23] [Chemical formula 24] 9. The chemical adsorption film is a monomolecular film.
9. The method for producing an ion conductive thin film according to any one of 8 to 8. 10. The method for producing an ion conductive thin film according to claim 4, wherein the chemisorption film is a monomolecular cumulative film.